CN1191554A - 低收缩趋势的聚乙烯模塑组合物 - Google Patents

低收缩趋势的聚乙烯模塑组合物 Download PDF

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CN1191554A
CN1191554A CN96195675A CN96195675A CN1191554A CN 1191554 A CN1191554 A CN 1191554A CN 96195675 A CN96195675 A CN 96195675A CN 96195675 A CN96195675 A CN 96195675A CN 1191554 A CN1191554 A CN 1191554A
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P·纽曼
S·韦伯
D·莱尔杰
H－H·戈茨
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Abstract

由以下组成的基于乙烯聚合物的模塑组合物(A)40到65%重量的乙烯聚合物,其密度从0.948到0.964g/cm3,熔融流动指数(MFI)从6到20g/10分钟,并且平均分子量分布Mw/Mn从2到5,(B)35到60%重量的乙烯聚合物,其密度从0.935到0.953g/cm3,熔融流动指数(MFI)从0.1到0.35g/10分钟,并且平均分子量分布Mw/Mn从6到20,和(C)0到6%重量的热塑性塑料常用添加剂,其中,模塑组合物的密度从0.948到0.957g/cm3,熔融流动指数从1.0到2.0g/10分钟,平均分子量分布Mw/Mn从3到10,并且组分(A)和(B)的密度差△D(△D=D(A)－D(B))从0到0.029g/cm3。

Description

低收缩趋势的聚乙烯模塑组合物
本发明涉及由以下组成的基于乙烯聚合物的模塑组合物：
(A)40到65％重量的乙烯聚合物，其密度从0.948到0.964g/cm3，熔融流动指数(MFI)从6到20g/10分钟并且其平均分子量分布Mw/Mn从2到5，
(B)35到60％重量的乙烯聚合物，其密度从0.935到0.953g/cm3，熔融流动指数(MFI)从0.1到0.35克/10分钟，并且其平均分子量分布Mw/Mn从6到20，和
(C)0到6％重量的热塑性塑料常用添加剂，
其中模塑组合物的密度从0.948到0.957g/cm3，熔融流动指数(MFI)从1.0到2.0克/10分钟，平均分子量分布Mw/Mn从3到10，并且组分A和B的密度差(ΔD＝D(A)-D(B))从0到0.029g/cm3。
本发明还涉及通过熔融挤出制备这种模塑组合物的方法，用模塑组合物制备薄膜，纤维和成型件的用途，还涉及用这种模塑组合物制备的薄膜、纤维和成型件以及制备的螺旋密封件。
基于乙烯聚合物的混合物，下述称聚乙烯共混物已被人们认识和应用，例如，如DE-C 34 37 116所述，用来制备抗应力开裂的成型件。
在最近，聚乙烯共混物被用来注射成型多种螺旋密封件。如果在注射成型后，即在冷却过程中，螺旋成型件保持它们的尺寸和形状，即不收缩(低收缩率)，这将是有利的。如果聚乙烯模塑组合物具有好的熔融流动性，通常使注射模塑变得容易。低的收缩率和形状稳定性是塑料应用中的一个重要性能，例如，制备精密配合的螺旋密封件。
已知的模塑组合物，一方面它的尺寸和形状稳定性(收缩行为)及另一方面好的流动性的综合性能并不让人十分满意。
本发明的目的是克服这些缺点并特别提供同时具有好的流动性和好的尺寸以及形状稳定性(低收缩率)的聚乙烯模塑组合物。
我们发现，通过以下几方面可以达到这一目的：开头定义的模塑组合物，它们的制备方法，它们用于制备薄膜、纤维、和成型件的用途，用这种模塑组合物生产的薄膜、纤维和成型件，以及用它生产的螺旋密封件。
这种新型模塑组合物含有作为组分(A)的以乙烯聚合物为基准的40到65％重量，优选55到60％重量的以下特征的乙烯聚合物，其密度按DIN53 479测量从0.948到0.964g/cm3，优选0.959到0.964g/cm3，熔融流动指数按DIN53 735在190℃和2.16kg负荷下测量从6到20g/10分钟，优选6到10g/分钟，且其平均分子量分布Mw/Mn用GPC方法，在135℃在1，2，4-三氯苯中测定(聚乙烯标准)，是从2到5，特别从3到4。
组分(A)通常是在本领域技术人员熟知的、例如DE-A 34 33 468，特别是实施例1已知的Ziegler催化剂的存在下，通过乙烯聚合或乙烯与C3-C12-1-链烯共聚得到。乙烯/1-链烯共聚物最多含有0.1％重量，优选最多0.5％重量的由1-链烯形成的结构单元。优选使用一种或多种C3-C8-1-链烯类的共聚单体，例如丙烯、1-丁烯、1-戊烯、1-己烯和1-辛烯。
新型模塑组合物含有作为组分(B)的以乙烯聚合物为基准的35到60％重量，优选40到45％重量的以下特征的乙烯聚合物，其密度按DIN 53 479测定是从0.935到0.953g/cm3，优选0.935到0.941g/cm3，其熔融流动指数按DIN 53 735在190℃和2.16kg负荷下测定是从0.1到0.35g/10分钟，优选0.1到0.2g/10分钟，并且它的平均分子量分布Mw/Mn，用GPC在135℃在1，2，4-三氯苯(聚乙烯标准)测定，是从6到20，特别从8到15。
组分(B)一般在本领域技术人员熟知的、例如在DE-A25 40 279中，特别是实施例中已知的Phillips催化剂存在下，由乙烯聚合或乙烯与C3-C12-1-链烯共聚得到。
用作组分(B)的乙烯/1-链烯共聚物含有0.5到3％重量，优选0.5到2％重量的由1-链烯形成的结构单元。优选使用一种或多种C3-C8-1-链烯类共聚单体，例如丙烯、1-丁烯、1-戊烯、1-己烯和1-辛烯。
新型模塑组合物还可以含有以乙烯聚合物为基准的0到6％重量，优选0.1到1％重量的热塑性塑料常用添加剂。适合本发明的特别有：润滑剂(硬脂酸钙)，常规稳定剂，例如苯酚，亚磷酸盐，二苯酮，苯并三唑，硫醚；填料，例如TiO2，白垩和炭黑，以及常规的颜料，如TiO2和群青蓝。
新型模塑组合物的密度按DIN 53 479测定在0.948到0.957g/cm3，优选0.948到0.954g/cm3之间。
新型模塑组合物的熔融流动指数，按DIN 53 735，在190℃和2.16kg负荷下测定，在1.0到2.0g/10分钟之间。
新型模塑组合物的平均分子量分布Mw/Mn用凝胶渗透色谱(GPC)，按照聚乙烯标准，在1，2，4-三氯苯中和135℃下测定，在3到10，优选4到8之间。
用来生产新型模塑组合物的组分(A)和(B)的密度差ΔD(ΔD＝D(A)-D(B))从0到0.029g/cm3，优选0到0.024g/cm3之间。
新型模塑组合物由组分(A)、(B)和需要时的(C)的制备是用塑料加工工艺中常用的方法，如熔融挤出，塑炼，密实或溶液混合来混合这些组分。优选用熔融挤出方法，例如用双螺杆挤出机。挤出温度一般在140到250℃之间。
组分加入的先后次序一般并不重要。所以可以将组分(A)、(B)和需要时的(C)预先混合后加入混合设备，或将它们分别加入，或需要时，可以将预先混合的两组分与第三组分分别加入。
新型模塑组合物的流动性能用注射模塑试验来测定(螺旋流试验)。为此，测量是通过适当的乙烯聚合物填充螺旋结构的注射模具来完成的(试验规范10和10.1，BASF AG：加工温度270℃，循环周期30秒，螺旋长度以厘米计)。
新型模塑组合物的尺寸和形状稳定性是用类似于BASF试验方法第12的方法测定的。为此，在注塑机中用螺纹模(螺纹直径28.2毫米)在180到270℃制备塑料密封件，进行冷却，测定50个试样的螺纹外直径，以毫米为单位计算平均值，计算与螺纹模直径的差值，目测衡量试样的尺寸和形状稳定性。
新型模塑组合物同时具有好的流动性能(螺旋长度大于20厘米)以及好的尺寸和形状稳定性(低收缩率)。它们尤其适用于进一步加工生产螺纹密封件，例如饮料瓶。
实施例1至5
聚合物共混物由下列列举的乙烯聚合物(A)(乙烯均聚物)和(B)(乙烯/1-己烯共聚物，1-己烯含量2.5％重量)与以乙烯聚合物为基准的0.3％重量的硬脂酸钙和IrganoX1076作为稳定剂，用双螺杆挤出机(Werner&Pfleiderer ZSK 53)在下列挤出条件下制备；测定它们的性能(见表1)，并用它们来注射成型为密封件。
挤出条件：
聚合物产率：50kg/小时
转速：120/分钟
熔融温度：200℃
乙烯均聚物(A)：
催化剂：Ziegler(DE-A 34 33 468，实施例1)MFI[g/10分钟](190℃/2.16kg)：8.2密度[g/cm3]：0.9615Mw 1)：80,000Mw/Mn 1)：4乙烯/1-己烯共聚物(B)：催化剂：Phillips(DE-A 25 40 279，实施例)MFI[g/10分钟](190℃/2.16kg)：0.15密度[g/cm3]：0.9372Mw 1)：200,000Mw/Mn 1)：9
1)  用凝胶渗透色谱测定
(1，2，4-三氯苯，135℃，PE标准)表1由组份(A)和(B)制备的聚乙烯模塑组合物及其性能
    混合物     混合物     混合物     混合物    混合物
实施例     1     2     3     4     5
比值1)(B)∶(A)     40/60     42.5/57.5     45/55     47.5/52.5     50/50
MFI(g/10)(190℃/2.16kg)     1.79     1.56     1.52     1.37     1.23
密度(g/cm3)     0.9520     0.9515     0.9518     0.9512     0.9502
螺旋长度270℃(cm)     28.9     29.1     28.8     28.6     29.7
螺纹直径(mm)平均值最小值最大值 28.1928.1828.20 28.2028.1928.23 28.2428.2328.25 28.1828.1828.19 28.2528.2328.26
Mw     -     139      -     -     141
Mn     -     25      -     -     21
Mw/ Mn     6     7
1)以重量百分比计，以乙烯聚合物为基准。

Claims (10)

1.由以下组成的基于乙烯聚合物的模塑组合物：
(A)40到65％重量的乙烯聚合物，其密度从0.948到0.964g/cm3，熔融流动指数(MFI)从6到20g/10分钟，且平均分子量分布Mw/Mn从2到5，
(B)35到60％重量的乙烯聚合物，其密度从0.935到0.953g/cm3，熔融流动指数(MFI)从0.1到0.35g/10分钟，且平均分子量分布Mw/Mn从6到20，和
(C)0到6％重量的热塑性塑料常用添加剂，
其中模塑组合物的密度从0.948到0.957g/cm3，熔融流动指数(MFI)从1.0到2.0g/10分钟，平均分子量分布Mw/Mn从3到10，并且组分(A)和(B)的密度差ΔD(ΔD＝D(A)-D(B))从0到0.029g/cm3。
2.如权利要求1所述的模塑组合物，其中组分(A)占55到60％重量，组分(B)占40到45％重量。
3.如权利要求书1所述的模塑组合物，其中组分(A)的密度从0.959到0.964g/cm3，组分(B)的密度从0.935到0.941g/cm3。
4.如权利要求1至3中所述的模塑组合物，其中组分(A)的熔融流动指数(MFI)从6到10g/10分钟，组分(B)的熔融流动指数从0.1到0.2g/10分钟。
5.如权利要求1至4所述的模塑组合物，其中组分(A)是含有最多1％重量的化学键合的1-链烯单元的乙烯/1-链烯共聚物，组分(B)是含有0.5到3％重量的化学键合的1-链烯单元的乙烯/1-链烯共聚物，其中1-链烯是C3-C12-1-链烯。
6.一种在0到6％重量的热塑性塑料常用添加剂存在下，用熔融挤出方法生产如权利要求1至5中所述的基于乙烯聚合物的模塑组合物的方法，其中组分(A)是用Ziegler催化剂制备，组分(B)是用Phillps催化剂制备。
7.用权利要求1至5中所述的模塑组合物生产纤维、薄膜和成型件的用途。
8.用权利要求1至5中所述的模塑组合物生产螺旋密封件的用途。
9.由权利要求1至5中所述的模塑组合物生产的薄膜、纤维和成型件。
10.由权利要求1至5中所述的模塑组合物生产的螺旋密封件。
CN96195675A 1995-07-19 1996-07-05 低收缩趋势的聚乙烯模塑组合物 Expired - Fee Related CN1070209C (zh)

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CN108368644A (zh) * 2015-12-10 2018-08-03 陶氏环球技术有限责任公司 用于制备带材、纤维或单丝的聚乙烯组合物

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ES2133195T3 (es) 1999-09-01
EP0839164A1 (de) 1998-05-06
KR19990029057A (ko) 1999-04-15
CN1070209C (zh) 2001-08-29
JPH11509568A (ja) 1999-08-24
ATE180504T1 (de) 1999-06-15
EP0839164B1 (de) 1999-05-26
KR100440701B1 (ko) 2004-10-14
JP3848682B2 (ja) 2006-11-22
WO1997004025A1 (de) 1997-02-06
US5981664A (en) 1999-11-09
DE59602011D1 (de) 1999-07-01

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